O-cycloalkyl-s-alkyl-o-halophenyl-phosphorothiolates

ABSTRACT

O-ALKYL(-CYCLOALKYL)-S-ALKYL-O-HALOPHENYL-PHOSPHOROTHIOLATES, I.E. O-ALKYL AND CYCLOALKYL-S-ALKYL-O-CHLORO-AND BROMO-SUBSTITUTED-PHENYL- E- PHOSPHOROTHIOLATES OR -THIOLPHOSPHAGES, WHICH POSSESS FUNGICIDAL PROPERTIES AND WHICH MAY BE PRODUCED BY CONVENTIONAL METHODS.

United States Patent 3,663,665 0-CYCLOALKYL-S-ALKYL-0-HALOPHENYL-PHOSPHOROTHIOLATES Toyohiko Kume and Shizuo Higashikawa, Tokyo, Japan,assignors to Farbenfabriken Bayer Aktiengesellschaft,

Leverkusen, Germany No Drawing. Filed June 3, 1969, Ser. No. 830,133Claims priority, application Japan, June 18, 1968, 43/ 41,619 Int. Cl.C07f 9/18; A01n 9/36 U.S. Cl. 260-958 2 Claims ABSTRACT OF THEDISCLOSURE O-alkyl(-cycloalkyl)-S-alkyl-O-halophenyl phosphorothiolates,i.e. O-alkyl and cycloalkyl-S-alkyl-O-chloro-andbromo-substituted-phenyl- -phosphorothiolates or thiolphosphates, whichpossess fungicidal properties and which may be produced by conventionalmethods.

Heretofore, in controlling serious rice diseases such as blast andsheath blight, organic mercury compounds and organic arsenic compoundssuch as phenyl mercuric acetate (A), methyl arsonic acid, salts, etc.,which contain heavy metals harmful to man and cattle have been usedwidely, because they are excellent in their fungicidal effect and arecomparatively economical to use. However, the use of organic mercuriccompounds during the growing period of rice plants is objectionable froma public health standpoint because of the direct and indirect toxicityof these known compounds to mammals.

Accordingly, inexpensive and effective compounds which do not containany heavy metals harmful to man and cattle are urgently needed to combatrice diseases.

It has now been found, in accordance with the present invention, thatthe particular new O-alkyl(-cycloalkyl)-S- alkyl-O-halo-phenyl-phosphorothiolates of the formula in which R is alkyl of 14 carbonatoms, R is alkyl of 1-6 carbon atoms or cycloalkyl of -6 ring carbonatoms,

X is halo, and n is a whole number from l-5 especially 3-4 exhibitstrong fungicidal properties.

In copending U.S. application Ser. No. 830,153, filed simultaneouslyherewith, corresponding to Japanese application Sho 41,618/68 and ofoverlapping inventorship herewith, O-alkyl(-cycloalkyl)-S-alkyl-Sphenyl-phosphorodithiolates are disclosed and claimed which possessfungicidal properties.

It has been furthermore found, in accordance with the present invention,that a process for the production of the particular new compounds ofFormula I above may be provided, which comprises (a) Reacting athiolphosphoryl halide of the formula in which R and R are the same asdefined above, and Hal is a halogen atom such as chloro, bromo or with aphenol of the formula III in which X and n are the same as definedabove, and

M is hydrogen or alkali metal such as sodium; or

(b) Reacting a phenyl-phosphorothiolate salt of the formula in which R,X and n are the same as defined above, and

M is alkali metal such as potassium, or ammonium, with an alkyl salt ofthe formula Y-R (V) in which R is the same as defined above, and

Y is halo or RSO (wherein R is the same as defined above).

Surprisingly, the particular new phosphorothiolates of Formula I aboveaccording to the present invention exhibit an excellent fungitoxiceffectiveness, especially for agricultural and horticultural purposes,more especially against rice diseases, and a certain insecticidaleffectiveness, with a comparatively low mammalian toxicity and aconcomitantly low phytotoxicity, whereas the known organic mercury andorganic arsenic compounds used for these purposes as aforesaid arehighly toxic to mamamls. Therefore, the instant compounds represent avaluable contribution to the art.

The general processes for the preparation of the instant compounds areillustrated by the folowing corresponding reaction schemes:

(III) The starting materials to be used for producing the instant newcompounds are already known and are clearly characterized by thecorresponding Formulae II, III, IV and V noted above.

Advantageously, in accordance with the present invention, in the variousformulae herein:

R represents lower alkyl hydrocarbon of 1-4 carbon atoms such as methyl,ethyl, nand isopropyl, n-, iso-, sec.- and tert.- butyl, and the like,especially C or C alkyl;

R represents lower alkyl hydrocarbon of 1-6 carbon atoms such as methyl,ethyl, nand iso-propyl, n-, iso-, sec.- and tert.- butyl, nand iso-amyl,nand iso-hexyl, and the like, especially C or C or C alkyl; orcycloalkyl hydrocarbon of -6 ring carbon atoms such as cyclopentyl,cyclohexyl, and the like, especially cyclohexyl;

X represents halo such as chloro, bromo, fluoro and iodo, especiallychloro and bromo;

n represents a whole number from 1 to 5, especially 3 to 4;

X, when n is 1-5, being in 2-, 3- or 4- mono; 2,3-, 2,4-, 2,5-, 2,6,3,4- or 3,5- di; 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-. 2,4,6- or 3,4,5-tri;2,3,4,5-, 2,3,4,6- or 2,3,5,6-tetra; and penta -halo (i.e. same or mixed-chloro, -bromo, -fluoro and/ or -iodo) -position, i.e. on the phenylnucleus;

Hal represents halo such as chloro, bromo, fluoro and iodo, especiallychloro;

M represents hydrogen; or an alkali metal atom such as sodium,potassium, lithium, and the like, especially sodium and potassium;

M represents an alkali metal atom as defined above, especiallypotassium; or an ammonium group; and

Y represents halo as defined above, especially chloro; or RSC wherein Ris the same as defined above.

Preferably, R is C alkyl; R is C alkyl or cyclohexyl; X is chloro 0rbromo; and n is 1-5 or 3-4; espe cially with X being the same halo whenn is more than 1. Such compounds possess an excellent effect againstserious rice diseases such as blast, brown spot and sheath blight.

As examples of thiolphosphoryl halides of formulae (II) above which maybe used as starting materials, there are mentioned: O-n-butyl-S-methyl,O-n-butyl-S-ethyl-, O-n-butyl-S-sec.-butyl-, O-n-hexylS-ethyl-,O-isopropyl-S- methyl-, O-isopropyl-S-ethyl-, O-isopropyl-S-n-butyl-, O-ethyl-S-methyl-, O-ethyl-S-ethyl-, O-cyclohexyl-S-methyl-,O-cyclohexyl-S-ethyl, O-cyclohexyl-S-n-butyl-, and the like,thiolphosphoryl chlorides, bromides, etc.

As examples of phenols and corresponding alkali metal salts of FormulaIII above which may be used as starting materials, there are mentioned:phenol, 2-, 3- and 4- mono'-; 2,3-, 2,4-, 2,5-, 2,6, 3,4- and 3,5- di-;2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- and 3,4,5- tri-; 2,3,4,5-,2,3,4,6- and 2,3,5,6-tetra-; and penta-chloro, bromo, fluoro and/oriodo, especially chloro and bromo-substituted phenols, and thecorresponding sodium and potassium phenates, and the like.

As examples of phenyl-phosphorothiolate salts of Formula IV above whichmay be used as starting materials there are mentioned: O-(methyl, ethyl,n-propyl, isopropyl, n-butyl, n-hexyl and cyclohexyl)-O-(2-, 3- and4-mono-; 2,3-, 2,4-, 2,5-, 2,6, 3,4- and 3,5- cli-; 2,3,4-, 2,3,5-,2,3,6-, 2,4,5-, 2,4,6- and 3,4,5- tri-; 2,3,4,5-, 2,3,4,6- and 2,3,5,6-tetra-; and penta- -chloro, bromo, fluoro and iodo-substitutedphenyl)-phosphorothiolatesodium, potassium and ammonium salts, and thelike.

As examples of alkyl salts of Formula V above which may be used asstarting materials, there are mentioned: methyl, ethyl, n-propyl,isopropyl, n-butyl, iso-butyl, sec.- butyl and tert.-butyl -chloride,-bromide, -fluoride and -iodide, and the like, and di-methyl, ethyl,n-propyl, isopropyl, n-butyl, iso-butyl, see-butyl andtert.-butyl-sulfate, and the like.

Suitable inert organic solvents usable for carrying out the productionprocess in accordance with both reaction variant (a) and reactionvariant (b) of the present invention include hydrocarbons, such asbenzene and benzine; chlorinated hydrocarbons, such as methylenechloride, ethylene chloride, carbon tetrachloride and dichlorobenzene;alcohols such as methanol, ethanol, propanol and butanol; ethers, suchas diethyl ether, dibutyl ether and dioxan; ketones, such as acetone,cyclohexanone and methylethyl ketone; and acetonitrile and dimethylformamide; and the like.

The reaction temperature for both reaction variant (a) and reactionvariant (b) can be varied within a fairly wide range. In general, thereaction is carried out at substantially between about 0100 C.,preferably between about 080 C.

A basic substance, preferably a tertiary amine, such as triethylamine,pyridine, dimethyl-cyclohexylamine, dimethylaniline anddimethylbenzylamine, is advantageously employed as acid binding agentwhere the corresponding free starting phenol is used according toreaction variant (a).

When carrying out the production process, approximately equimolaramounts of the starting reactants are used, but an excess of the acidbinding agent is not harmful, i.e. where the free phenol is usedaccording to re action variant (a). An inert organic solvent such asbenzene (e.g. reaction variant (a)) or ethanol (e.g. reaction variant(b)) may be employed and the reaction may be carried out, for example,in triethylamine as acid binding agent where the free starting phenol isused according to reaction variant (a). A temperature of about 080 C.may be used, and the reaction effected by dissolving the phenol andtriethylamine in benzene and adding the thiolphosphoryl halide dropwisethereto according to reaction variant (a), or by dissolving thephenyl-phosphorothiolate salt in ethanol and adding the alkyl halide oralkyl sulfate thereto according to reaction variant (b).

After completion of the reaction (about l-6 hours), the reaction mixturemay be worked up in the usual manner, such as by washing the organicphase of the reaction mixture With water and thereafter with aqueoussodium carbonate solution and water, then drying with anhydrous sodiumsulfate, and distilling off the benzene, e.g. according to reactionvariant (a); or by filtering off the solids, distilling off the ethanolfrom the filtrate, dissolving the residue in benzene, washing withaqueous sodium carbonate solution, drying with anhydrous sodium sulfate,and distilling off the benzene, e.g. according to reaction variant (b).The residue is in most cases a colorless oil which is soluble in organicsolvents and only slightly soluble in water.

Advantageously, the particular new active compounds according to thepresent invention exhibit strong fungitoxic activity and aredistinguished by a broad spectrum of activity. Their low toxicity towarm-blooded animals and their good compatibility with higher plantspermits the instant new compounds to be used as plant protection agentsagainst fungal plant diseases. In the concentrations normally used forthe control of fungi, the instant compounds do not damage cultivatedplants.

'Fungitoxic agents, such as the instant compounds, are usable in plantprotection, i.e. agricultural and horticultural endeavors, for thecontrol of fungi from the most diverse classes of (fungi, such asArchimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and F ungiImperfecti.

The particular new active compounds according to the present inventioncan be used for example against parasitic fungi, on above-the-soil partsof plants, fungi which cause tracheomycosis which attack the plant fromthe soil, seed-borne fungi and soil-inhabiting fungi.

By reason of their excellent properties mentioned above, the particularnew active compounds according to the present invention can also be usedWith good results against fungal diseases which hitherto had to becontrolled with fungicidal agents containing heavy metals harmful to manand cattle, e.g. arsenic and mercury.

The instant active compounds have given particularly good results in thecontrol of serious rice diseases including not only rice blast and brownspot, but also sheath blight. Thus, the instant compounds show anexcellent activity against the fungi Piricularia oryzae (i.e. blast),Cochliobolus miyabeansu (i.e. brown spot) and Pellicularia sasakii (i.e.sheath blight), as Well as against the fungi Mycosphaerella melonis(cucumber) Alternia kikuchiana (pear), Elsinoe ampeliva (grape), and thelike.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert pesticidal diluents or extenders, i.e. conventionalpesticidal dispersible carrier vehicles, such as solutions, emulsions,suspensions, emulsifiable concentrates, spray powders, pastes, solublepowders, dusting agents, granules, etc. These are prepared in knownmanner, for instance by extending the active compounds with conventionalpesticidal dispersible liquid diluent carriers and/or dispersible solidcarriers optionally with the use of carrier vehicle assistants, e.g.conventional pesticidal surface-active agents, including emulsifyingagents and/or dispersing agents, whereby, for example, in the case wherewater is used as diluent, organic solvents may be added as auxiliarysolvents. The following may be chiefly considered for use asconventional carrier vehicles for this purpose: inert dispersible liquiddiluent carriers including inert organic solvents and non-solvents, suchas aromatic hydrocarbons (e.g. benzene, toluene, xylene, dimethylnaphthalene, aromatic naphthas, etc.), halogenated, especiallychlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.),paraffins (e.g. petroleum fractions), chloroinated aliphatichydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g. methanol,ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.),ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.), amides(e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide,etc.) ketones (e.g. acetone, etc.), and/or water; as well as inertdispersible finely divided solid carriers, such as ground naturalminerals (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonate,talc, kieselguhr, diatomaceous earth, clay, montomorillonite, etc.), andground synthetic minerals (e.g. highly dispersed silicic acid,silicates, e.g. alkali silicates, etc.); whereas the following may bechiefly considered for use as conventional carrier vehicle assistants,e.g. surface-active agents, for this purpose: emulsifying or wettingagents, such as nonionic and/or anionic emulsifying or wetting agents(e.g. polyethylene oxide esters of fatty acids, polyethylene oxideethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., andespecially alkyl aryl-polyglycol ethers, magnesium stear-ate, sodiumoleate, etc.); and/or dispersing agents, such as lignin, sulfite wasteliquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/ or liquid dispersiblecarrier vehicles and/ or with other known compatible active agents,especially plant protection agents, such as other fungicides, orherbicides, insecticides, acaricides, nematocides, bactericides, etc.,including, especially organo-phosphorus compounds, chlorine compounds,compounds, dithiocarbamate compounds, chlorine compounds, dinitrocompounds, organic sulfur or copper compounds, substituted phenoxycompounds, chlorophenols, substituted diphenyl ethers anilide compounds,ureas, triazines, antibiotics, and other known agricultural chemicalsand/or fertilizers, if desired, or in the form of particular dosagepreparations for specific application made therefrom, such as solutions,emulsions, suspensions, powders, pastes, and granules which are thusready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-95%, and preferably05-90%, by weight of the mixture, whereas carrier composition mixturessuitable for direct application or field application generallycontemplate those in which the active compound is present in an amountsubstantially between about 0.00l-l0%, preferably ODS-5%, by weight ofthe mixture. Thus, the present invention contemplates over-allcompositions which comprise mixtures of a conventional dispersiblecarrier vehicle such as (1) a dispersible inert finely divided carriersolid, and/or (2) a dispersible liquid such as an inert organic solventand/ or water preferably including a surface-active effective amount ofa carrier vehicle assistant, e.g. a surface-active agent, such as anemulsifying agent and/or a dispersing agent, and an amount of the activecompound which is effective for the purpose in question and which isgenerally between about 0.001-%, and preferably 0.05- 95 by weight ofthe mixture.

Generally, the active compound is used in dosage amounts per unit areaof substantially between about 15- 1000 preferably 40-600 g. and mostpreferably 40-100, per 10 ares, irrespective of the presence or absenceof such carrier vehicle.

The active compounds can also be used in accordance with the well-knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment in finelydivided form, e.g. average particle diameter of from 50-100 microns; oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 1 quart/acre, preferably 2-16 fluidounces/acre, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95% by weight of the activecompound, or even the active substance alone, e.g. about 20-100% byweight of the active compound.

In particular, the present invention contemplates methods of selectivelykilling, combating or controlling fungi, which comprise applying to atleast one of (a) such fungi and (b) their habitat, i.e. the locus to beprotected, a fungicidally effective or toxic amount of the particularactive compound of the invention alone or together with a carriervehicle as noted above. The instant formulations or compositions areapplied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, Watering, sprinkling, pouring,dressing, via incrustation, and the like.

Significantly, the fungicidal compositions of the present invention canbe applied for example by spraying a dust formulation directly ontostems and leaves of plants; or by using the formulation forseed-dressing; by spraying an emulsifiable concentrate, diluted withwater, etc. to a desirable concentration, onto stems and leaves ofplants; by suspending a wettable powder in water at a desirableconcentration and spraying the formulation onto stems and leaves ofplants; by applying granule formulations to soil; and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application, the purpose for which the activecompound is used, and the like. Therefore, in special cases, it ispossible to go above or below the aforementioned concentration rangesand dosage amounts per unit area.

The following illustrate, without limitation, examples of formulationswhich may be used in accordance with the present invention:

Formulation A 15 parts of instant compound (11), 80 parts of a mixtureof diatomaceous earth and kaolin (1:5) and 5 parts of the emulsifierRunox (trade name of the product of Toho Kagaku Kogyo K.K., Japan), i.e.polyoxyethylenealkylarylether, are formulated into a wettable powder bycrushing and mixing. It is diluted with water at the con centration of 1to 300-500 and applied by spraying to the phytophathogenic fungi and/ortheir habitat.

Formulation B 30 parts of instant compound (3), 30 parts of xylene and30 parts of Kawakazol (trade name of the product of Kawasaki Kasei KogyoK.K., Japan), i.e. aromatic hydrocarbons of high boiling point, and 10parts of the emulsifier Sorpol (trade name of the product of Toho KagakuKogyo K.K., Japan), i.e. polyoxyethylenealkylarylether, are formulatedinto an emulsifiable concentrate by mixing and stirring. It is dilutedwith water to the concentration of 1 to 1000 and applied by spraying tothe phytopathogenic fungi and/ or their habitat.

Formulation C 2 parts of instant compound (8) and 98 parts of a mixtureof talc and clay (3:1) are formulated into a dust by crushing andmixing. It is applied as is by dusting to the phytopathogenic fungiand/or their habitat.

Formulation D 1.5 parts of instant compound (11), 1.5 parts of O-ethyl-S,Sdiphenyl-phosphorodithiolate, and 97 parts of a mixture of talcand clay (3:1) are formulated into a dust by crushing and mixing. It isapplied in the same manner described in Formulation C.

The fungicidal effectiveness of the particular new compounds of thepresent invention is illustrated without limitation, by the followingexamples:

EXAMPLE 1 Test against rice blast (Piricularia orvzae) (Pot test) Paddyrice (Jukkoku variety) was cultivated in pots of 12 cm. in diameter andthe diluted aqueous solution of the particular active compound in theformulation of wettable powder as described in Formulation A was sprayedon the rice plants at their young ear forming stage until leaves of riceplants became dripping wet. On the next day the sprayed (i.e. treated)rice plants were placed in a moisture chamber and kept there underconditions of the relative hiumity of 100% at the temperature of 25 C."for 48 hours. During that time a spore suspension of rice blast(Piricularia oryzae) pathogen was sprayed onto two time for inoculation.After the inoculated rice plants were kept under such conditions for 7days, the disease attack rate, i.e. infestation, per pot was evaluatedand classified according to the rating from to 5, and the controllingvalue against blast was calculated from the following formula:

Disease attack rate Percentage of disease- (Infestation): spot area 0 0Controlling value Infestation in non-treated plot I. in treated plotInfestation in non-treated plot The particular active compounds tested,their concentrations and the results obtained (rate of attack on thebasis of the mean value of 5 plots per compound tested) can be seen fromthe following Table 1.

TABLE 1 Test results of fungicidal effect against rice blast [Pot test]Concentration of active Controlcompound Iuiestaling Phyto- Activccompound No. in p.p.m. tion value toxicity Compounds of invention:

500 1. 9 500 1. 2 250 O. 9 500 2.2 500 1. 5 500 2. 2 500 2. 2 250 1.0500 2.0 500 1.4 250 0.7 500 2. 2 500 1.0 500 2. 2 500 2.8 (161 500 2. 5O-n-butyl-S-ethyl-O- plicnyl-phosphorotliiolate (comparison) 500 4.7Known compound comarisen: (A PMA (Phenylmereuric acetate) 20 1. 0 (i8O-cthyl-S-etl1yl-O-(4- ehlorophenyl)-phospliorothiolate 500 4. 3 1iControl 5.0 0

Norm-Compounds of invention have corresponding numbers to those of Table3 and Example 3 below, as the case may be.

EXAMPLE 2 Test against plant pathogens (Agar dilution method) Theparticular active compound is mixed in an agar culture medium of potatoto form the desired concentration of active compound therein. After themedium is poured into Petri dishes of 9 cm. in diameter and coagulated,the same are inoculated with the corresponding plant pathogens. StandardPetri dishes to which preparations of the active compound of Zineb(Zinc-ethylene bisdithiocarbamate) are added are also set up. Afterhaving been cultured at 27 C. for 4 days, the growth condition of theplant pathogens is investigated and the minimum concentration of theactive compound (in p.p.m.) for growth inhibition is determined.

The particular active compounds tested and the results obtained (i.e.the minimum concentration in p.p.m. for growth inhibition) can be seenfrom the following Table 2.

TABLE 2 Test result of fungicidal effect. against various plantpathogens [Agar dilution method] Parts per million Cochlia- Alter-Piricubolus Pcllicunarz'a laria miyalaria kikuchi- Elsinoe Active or zacbeanua sasakz'i ana ampclina compound No. (rice) (rice) (rice) (pear)(grape) 20 50 50 50 20 50 100 50 50 20 25 100 25 5O 20 50 100 50 50 1050 100 50 50 20 50 100 100 50 20 50 100 100 50 2O 50 50 50 50 50 100 5050 10 100 50 100 20 100 100 50 20 50 50 100 20 50 100 100 (141) 20 25100 100 100 Zineb (Standard). 50 200 100 200 200 Norm-Compounds oiinvention have corresponding numbers to those of Table 3 below, as thecase may be.

The following further examples illustrate, without limitation, theprocess for producing the particular new compounds of the presentinvention.

9 EXAMPLE 3 20 g. of 2,4,5-trichloro-phenol and 10.3 g. of triethylamineare dissolved in 300 ml. of benzene. To this solution, 20 g. ofO-n-butyl-S-methyl-thiolphosphoryl-chloride B.P. 72 C./0.2 mm. Hg) areadded dropwise while cooling. After the completion of the addition, themixtures is stirred for hours at 60 C. and then the reaction mixture iscooled. The organic layer is washed with water and then with 1% sodiumcarbonate solution and water and thereafter dehydrated over anhydroussodium sulfate. Upon distilling off the benzene present and thendistilling the residue further, 31 g. of colorless oily O-n-butyl-S-methyl O (2,4,5-trichlorophenyl)-phosphorothiolate, B.P. 165167 C./0.2mm. Hg, are obtained.

According to the same process, when O-n-butyl-S-secbutyl-thiolphosphorylchloride is reacted instead ofZO-nbutyl-S-methyl-thiolphosphorylchloride, O-n-butyl-S-secbutyl-O-(2,4,5-trichloro-phenylphosphorothiolate (17 with similar fungicidal activity is obtained. Oisopropyl- S n butyl-O-(2,4,5-trichloro-phenyl)-phosphorothiolate andO-n-butyl-S-methyl-O-(2,4,6-tribromo-phenyl)- phosphorothiolate (16 withsimilar fungicidal activity are also obtainable in analogous manner.

EXAMPLE 4 39 g. of the potassium salt ofO-n-butyl-O-(2,4,5-trichloro-phenyl)-phosphorothiolate are dissolved in200 ml. of ethyl alcohol. To this solution, 11 g. of ethylbromide areadded and the mixture is stirred for 4 hours at 60 C. After the reactionmixture has cooled, the formed precipitate is separated by filtrationand the solvent of the filtrate is distilled off. The remainingconcentrated residue is then dissolved in benzene. The benzene solutionis thereafter r washed with 1% aqueous solution of sodium carbonate anddehydrated over anhydrous sodium sulfate. Upon distilling 01f thebenzene present and further distilling the residue, 35 g. of colorlessoily O-n-butyl-S-ethyl-O-(2,4,5- trichlorophenyl)-phosphorothiolate,B.P. 168170 C./ 0.1 mm. Hg, are obtained.

According to the same process, when the corresponding potassium salt ofO-n-butyl-0-(4-chloro-phenyl) phosphorothiolate,O-n-butyl-O-(2,4-dichloro) phenyl)-phosphorothiolate andO-n-butyl-O-(2,4,6-tribromo phenyl)- phosphorothiolate respectively, isreacted instead of the potassium salt of O-n-butyl-O-(2,4,5-trichlorophenyl)- phosphorothiolate, the corresponding O-n-butyl-S-ethyl-O-halogeno-phenyl-phosphorothiolate with similar fungicidal activity isobtained, i.e.:

(18 O-n-butyl-S-ethyl-O-(4-chloro-phenyl)- phosphorothiolate (19O-n-butyl-S-ethyl-O-(2,4-dichlorophenyl)- phosphorothiolate (20O-n-butyl-S-ethyl-O-(2,4,6-tribromo-phenyl)- phosphorothiolate Thefollowing table 3 illustrates appropriate data for typical compounds ofthe present invention.

TABLE 2Coutinued These compounds may be designated:

(1 O-ethyl-S-methyl-O-(2,4,5-trichloro phenyl)- phosphorothiolate (2)O-isopropyl-S-methyl-O-(2,4,5-trichloro-pheriyl)- phosphorothiolate (3O-n-butyl-S-methyl-O-(2,4,5-trichloro-phenyl)- phosphorothiolate (4)O-n-butyl-S-methyl-O-(2,4,6-trichloro-phenyl)- phosphorothiolate (5O-n-butyl-S-methyl-O- (2,3,4,6-tetrachloro-phenyl)- phosphorothiolate(6) O-ethyl-S-ethyl-O-(2,4,5-trichloro-phenyl)- phosphorothiolate (7)O-ethyl-S-ethy1-O-(2,3,4,'6-tetrachloro-phenyl)- phosphorothiolate (8)O-isopropyl-S-ethyl-O- 2,4,5 -trichloro-phenyl)- phosphorothiolate (9)O-isopropyl-S-ethyl-O-(2,4,6-trichloro-phenyl)- phosphorothiolate 10)O-isopropyl-S-ethyl-O- (2,3 ,4,5-tetrachloro-phenyl phosphorothiolate(11 O-n-butyl-S-ethyl-O- (2,4,5-trichloro-phenyl)- phosphorothiolate 12)O-n-butyl-S-eth'yl-O- (2,4,6-trichloro-phenyl phosphorothiolate 13O-n-butyl-S-ethyl-O- (2,3,4,6-tetrachloro-phenyl phosphorothiolate 14)O-cyclohexyl-S-ethyl-O- (2,4,5-trichloro-pheny1) phosphorothiolateO-n-butyl-S-ethyl-O-(2,4,6-tribromo-phenyl)- phosphorothiolate It willbe realized by the artisan that all of the fore going compoundscontemplated by the present invention possess the desired strongfungicidal properties, with regard to a broad spectrum of activity, aswell as comparatively low toxicity toward warm-blooded creatures and aconcomitantly low phytotoxicit'y, enabling such compounds to be usedwith correspondingly favorable compatibility with warm-blooded creaturesand higher plants for more effective control and/ or elimination offungi by application of such compounds to such fungi and/ or theirhabitat.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

1. Phosphorothiolate of the formula in which R is alkyl of 14 carbonatoms, X is selected from chloro and bromo and n is a whole number from3-4. 2. Compound according to claim 1 wherein such compound isO-cyclohexyl-S-ethyl-O-(2,4,5-trichloro-phenyl)- phosphorothiolate ofthe formula References Cited UNITED STATES PATENTS 3,309,371 3/1967Curry et a1. 260-964 X JOSEPH REBOLD, Primary Examiner A. H. SUTTO,Assistant Examiner US. Cl. XJR- Farben 150 UNI'I'I'II S'F/VI'E'LSPA'EE'IN'F OFFICE Clflll'llFl CAT I, Oi! COi-llil SCH ON Patent No.3,665 Dated y a 1972 Inventor(SQ JLQIOhikQ Kum,e, g1; a!

It is certified that error appears in the move-identified patent andthat said Letters Patent are hereby corrected as shown below:

Col, '1, line 22, "(-cycloalikyl)" should be --(-cycloalkyl Col. 2,lille 38, insert --IV-- after the structural formuli Col. 5, line 8,"miyabeansu" should be --miyabeanus-- Col. 6, line 21, delete "g."after, "40-600" and after "40-100" ihsert -g.--

Col. 7, line 61, under "Infestation", fourth entry "1" should be --2-- ICol. 9, line 15, "mixtures" should be mixture-- Col. 10, line 4, Table3, after "meme" "15" should be --150-- Col. 10, line 26, 20" should be20-- Col. 10, line 55, formula (10 should be as follows I C1 Cl 0 c1 OP2 5 O-C H -i l c1 f Signed and sealed this 27th day of February 1973;

(SEAL) Attest:

' EDWARD M.-FLETCHER,JR. ROBERT GO'TTSCHALK Attesting OfficerCommissioner of Patents

